Nu-nitro-nu-trinitroalkylamine alcohols and derivatives thereof



2,987,549 N-NITRO-N-TRINITROALKYLAMINE ALCOHOLS AND DERIVATIVES THEREOF Henry Feuer, Lafayette, Ind., and William A. Swarts, Niagara Falls, N.Y.

No Drawing. Filed Oct. 16, 1958, Ser. No. 767,746 10 Claims. (Cl. 260-584) Our invention relates to novel nitro compounds and more particularly it relates to polynitro amino alcohols and to a process for producing same.

Our new compounds have the following structural formula:

R2 R3(|3R where R is the radical t -NR1C (N02) 3 R is selected from the group consisting of and alkylene having up to five carbon atoms; R is hydroxyalkyl having up to five carbon atoms; R is selected from the group consisting of hydrogen, alkyl having up to five carbon atoms; R is selected from the group consisting of hydrogen, alkyl having up to five carbon atoms, R-substituted alkyl, hydroxyalkyl having up to ten carbon atoms and R-and hydroxy-substituted alkyl having up to ten carbon atoms; and n is a number from 3 to 9.

Compounds which come within the above structural formula include: 2-(N-nitro-N-trinitroethylamino)-etha- 1101, 3 (N nitro-N-trinitroethylamino)-1-propanol, 2- methyl 2 (N-nitro-N-trinitroethylamino)-1,3-propanediol, 2-(N-nitro-N-trinitroethylamino)-1,4-butanediol, 2,3- bis(2-trinitroethylamino)-1,4-butanedoil, 2-propyl-2-[N- nitro N-(2-phenyl-2-trinitropropylamino)] 1,3-propanediol, 3-methyl-3-[N-nitro-N-(2-cyclohexyl-Z-trinitroethylamino)]heptanol, 6-(N-nitro-N-trinitroethylamino)-l-undecanol, 2- [N-nitro-N-(2-trinitrobutylamino) -1-pentanol, 2,6 bis[N-nitro-N-(2-phenyl-2-t1initroethylamino)]1,7- heptanedoil, 2,4-bis[N-nitro-N-(2-cyclopentyl-2-trinitroethylamino)]-2-ethyl-l-hexanol, 5,9-dihydroxymethyl-3,5, 9,1l-tetra(N-nitro-N-trinitroethylamino)tridecane, 2-hydroxybutyl 2,4-bis(N-nitro-N-trinitroethylamino)-l-hex anol, 2,9-diethy1-2,4,7,9-tetra[N-nitro-N-(2-trinitropropyl) amino]-1-l0-decanedoil, etc.

Generally our process for producing our new compounds consists of esterifying a nitrate having the following structural formula:

where R is the nitrate ester of hydroxyalkyl having up to five carbon atoms and R is selected from the group consisting of hydrogen, alkyl having up to five carbon atoms, R-stubstituted alkyl having up to ten carbon atoms, the nitrate ester of hydroxyalkyl having up to 10 carbon atoms and R and the nitrate ester of hydroxy substituted alkyl having up to 10 carbon atoms. The ester is in turn converted to the alcohol by subjecting it to acid hydrolysis. Our process appears to be operable for all nitrates of this type.

The nitrates untilized in forming the alcohols of our invention are easily prepared by the process of our copending application, U.S. Serial No. 713,512, now abandoned. In this application we claim a process wherein 1 Patents 2,582,048 and 2,548,803 wherein nitro substituted 7 2,987,549 Patented June 6, 1961 2 polynitroamino alcohols are nitrated to form the abovedescribed polynitroamino nitrate.

The nitration of the N-trinitroalkylamino alcohol is carried out using nitric acid as the nitrating agent, generally in the form of a nitrating mix with sulfuric acid, acetic anhydride, phosphorus pentoxide or other dehydrating agent which will not react with the reactants or products to destroy the desired nitrate. Generally we prefer to carry out the nitration reaction at temperatures ranging from about 5 to 25 C. Following completion of the nitration reaction, We can generally obtain the N- nitro-N-trinitroalkylaminoalkyl nitrate as a solid by cooling the reaction mixture to a temperature of about 0 or below as by pouring the reaction mixture over ice. The resulting product can be recrystallized by dissolving in cold fuming nitric acid and then cooling to the low temperatures indicated by any means, including pouring the nitric acid solution over ice.

The N-nitroN-trinitroalkylaminoalkyl nitrate can be converted to an N-nitro-N-trinitroalkylaminoalkyl ester by reacting the same with an esterifying agent such as acetic anhydride, phthalic anhydride, lower aliphatic acid chlorides, etc., in the presence of an acid esterification catalyst, such as sulfuric acid, benzenesulfonic acid, toluenesulfonic acid, etc. The reaction is carried out at low temperatures ranging from about 0 to about 30 C. The ester can ordinarily be recovered by cooling the reaction mixture to a temperature of about 0 or below as by pouring the reaction mixture over ice. Generally the ester is obtained as an oily liquid and it is generally desirable to dry the same by any convenient means such as, for example, dissolving the oily layer in ether, adding magnesium sulfate as a drying agent, removing the drying agent, and then removing the ether by distillation.

The N-nitro-N-trinitroalkylaminoalkyl ester can beconverted to the corresponding alcohol by hydrolysis in the usual manner. Acids such as hydrochloric, sulfuric, etc. can be employed and generally we prefer to employ reflux temperatures for carrying out the hydrolysis of the ester to obtain the alcohol. Generally We prefer to conduct the hydrolysis in the presence of an inert solvent, such as a lower alkyl alcohol. Following the reaction, the solvent can be removed by distilling in vacuo to obtainthe alcohol as an oily liquid which in some instances crystallizes upon cooling. to dissolve the oily product in a suitable solvent such as ether, and thenremove the solvent by distillation in vacuo to obtain a product oil which crystallizes upon cooling. In other instances, it is necessary to dissolve the oily product in a suitable solvent such as, for example, ether and then crystallize the same by addition of hexane or other suitable material to the ether solution. Ordinarily,

the product can be recrystallized from any suitable sol depending upon the chain length of the polymer, the" nature of the cross-linking agent, etc. These polymers are also stable to shock, heat, etc., to the extent that, as a general rule, additional stabilizers are not required in the propellant mixtures. Our monomers are also plasticizers for polymers prepared from our monomer alcohols.

As previously indicated, low molecular weight polymers preparedfrom the monomers of our invention are fluids. These propellants are generally rich in fuel elements and as such can be utilized as a fuel in the process of US. Patent 2,537,526 where tetranitromethane and hexani-T troethane are used as oxidants and liquid nitro parafiins are used as fuels; in the processes described in U.S.

In some instances it is necessary al-iphatic compounds having more than one nitro group per carbon atom were used as oxidants and nitro-substituted compounds having less than one nitro group per carbon atom were used as fuels in -monopropellantsysterns; or in the similar process of US. Patent- 2,590,009.

We have discovered that generally solid polymers 'prepared from our alcohols and various isocyanates and amines'can be dissolved in polar solvents, such as'i'dimethylformamide and lower nitro alkanes, such as tetranitromethane, and, as such, are operative as fuels 'in' the above-described processes. Other solvents which can be used to liquify our polymers include dimethylsulfoxide, Cellosolve, acetonitrile, lower alkanols, nitro esters and nitro ethers.

Rubber-like materials can be prepared by'interaction of our alcohols with cross-linking agents such as diisocyanates, variouspolycarboxylic'acids, such as succinic acid, tartaric acid, maleic acid, malic acid, etc.

Our monomers form polymers with tetranitrodicarboxylic acids which can be prepared-by interacting a tetranitro compound with methylacrylate, and hydrolyzing the resulting tetranitro ester to form'the acid.

a Our solid polymers can beimixed wih various oxidant salts, such as ammonium nitrate,'ammonium perchlorate,

lithium perchlorate, etc. to obtain solid heterogeneouspropellants having specific impulses on theorder of that of Ballistite.

The following examples are offered to illustrate the production of our new compounds. We do not intend to be limited to the specific materials, proportions, conditions, etc. shown, rather we intend to include all equivaients obvious to those skilled in the art.

Example I A solution composed of 10.5 grams of 2-methyl-2- amino-1,3-propanediol, 15.1 grams of trinitromethane, and 8.5 ml. of 37% formalin solution in 35 ml. of distilled water was prepared and held at ice 'bath temperature for several hours after which the water was removed by aerating the solution at 25 C. The residual oil was dissolved in ethyl alcohol and the solution dried over magnesium sulfate, after which the ethyl alcohol was removed by distillation in vacuo leaving 2-methyl-2-(N- trinitroethylamino)-1,3-propanediol as a heavy oil. The

oily product was dissolved in 50 ml. of acetic anhydride and the solution cooled to' 5 C. after which 30 ml. of fuming nitric acid was added to the'cooled solution over a period of one and one-half hours, the temperature being kept below 20 C. at all times. The mixture was then stirred at 5 to C. for two hours andpoured over crushed ice to precipitate 2-methyl-2-(N-nitro-N-trinitroethylamino)-1,3-propyl dinitrate as a heavy oil. The oily nitrate product was dissolved in 100 ml. of ether,-the solution washed with two 100 ml. portions of water'and driedwith magnesium sulfate after which the ether was removed in vacuo and the oily dinitrate dissolved in.100 ml. of acetic anhydride, cooled to 5 C. and stirred vigorously while 6 ml. of concentrated sulfuric acid was added insmall portions maintaining the temperature'blow C. The mixture was poured over crushed ice to give a red oil which was dissolved in 100 ml. of ethylene dichloride and the solution washed with water. and dried Withmagnesium sulfate. The solvent wasthen removed in vacuo to give a reddish impure solid which was triturated with methanol and the solid 2-methyl-2-(N-nitro-N trinitroethylamino)-1,3-propyl diacetate removed. Melting point 7575.5 C. Analysiscalculated: N=17.6; found: N=17.65. A 7.2 gram'portion of crude'2-methyl-2-(N- nitro-N-trinitroethylamino)-1,3-propyl diacetate was dissolved in a mixture of 100 ml. of methanol and 5 ml. of concentrated hydrochloric acid and the solution heated under reflux for two hours. Removal of the solvents in vacuo left a solid that was recrystallized from carbon terachloride to yield pure white Z-methyI-Z-(N-nitro-N- trinitroethylamino)-1,3-propanediol having a melting Example 11 Analysis- A mixture of ml. of concentrated sulfuric acid and 25 ml. of fuming nitricacid was cooled to approximately 15 C. and to the mixture was added 7.6-grams of 2-(N- trinitroethylamino)ethanol. The mixturewas stirred at 15-25 C. for approximately two hours after which it was poured over crushed ice to produce a solid that was purified by dissolving in cold fuming nitric acid followed by precipitation over crushed ice. The product was .dried in vacuo at 25-30 C. and recrystallized from ml. of ethylene dichloride. The product 2-(N-nitro-N-trinitro-. ethylamino)ethyl nitrate hada melting point of 105-106" C. with decomposition. Analysis-calculated: N=26.8; found: N=26.4. A 3-gram portion of Z-(N-nitro-N-trinitroethylamino)ethyl nitrate was dissolved in 30 ml. of acetic anhydride and the solution cooled and stirred vigorously. To the solution 3 ml. of concentrated sulfuric acid was added so that the temperature neverexceeded. 15 C. and after the addition of the acid was complete the mixture was allowed to stand for approximately 5 chloric acid and 30 gramsof crushed ice. had melted, the aqueous layer was washed with six 15 ml.

hours at 0-5 C. and then for an additional hour while the temperature rose to about 30 C. Themixture was then poured over crushed ice to obtain an oilwhi'ch was taken up in 100 ml. of ether, the solution washed with four 50 ml. portions of distilled water, dried over magnesium sulfate, and the ether then removed in vacuo to leave the oily 2-(N-nitro-N-trinitroethylamino) ethylacetate. The ester was dissolved in a mixture of 30 m1. of methanol and 3 ml. of concentrated hydrochloric acid and the solution refluxed for about two hours. The solvent was then removed in vacuo to leavean oil that solidifiedwhen two 10-15 ml. portions of etherwereadded and subsequently removed in vacuo. The materialwas recrystallized from carbon tetrachloride to-give- Z-(N-nitro- N-trinitroethylamino)ethanol as a white solid, melting point 74 C. Analysis-calculated: N=26.0%; found: N=26.2%.

The following example is ofiered to illustrate the conversion of our new N-nitro-N-trinitroalkylaminoalcohols into'further very powerful explosives.

Example III 'A 1.07 gram portion of Z-(N-nitro-N-trinitroethylamino) ethanol, 1.0 gram of 4,4,4-trinitrobutyryl chloride and 0.55 7 gram of aluminum chloride were dissolved in 30 m1. of ethylene dichloride and the solution heated at about 50 C. for-about 18 hours. The solution was then poured over amixture of 16 ml. of concentrated hydro- After the ice portions of ethylene dichloride and these extracts combined with the: originalethylenedichloride layer which wasthen washed with three 20 ml. portionsof water,

, dried with magnesium sulfate and concentrated'to 15 ml.

R is selected from the group consisting of orr- (CH1) ..-oHoH and al-kylene having up to five carbon atoms; R is hydroxyalkyl having up to five carbon atoms; R is selected from the group consisting of hydrogen, alkyl having up to five carbon atoms, hydroxyalkyl having up to five carbon atoms; R is selected from the group consisting of hydrogen, alkyl having up to five carbon atoms, R- substituted alkyl, hydroxyalkyl having up to ten carbon atoms; and n is a number from 3 to 9.

2. 2-(N-nitro-N-trinitroethylamino) ethanol.

3. 3-(N-nitro-N-trinitroethylamino)-1-propanol.

4. 2 methyl 2 (N-nitro-N-trinitroethylamino)-1,3- propanediol.

5. 2-(N-nitro-N-trinitroethylamino)-1,4-butanediol.

6. A process for the production of alcohols having the following structural formula R2 R -R 1%.

where R is the radical -NR -C (N02) 3 R is selected from the group consisting of and alkylene having up to five carbon atoms; R is hydroxyalkyl having up to five carbon atoms; R is selected from the group consisting of hydrogen, alkyl having up to five carbon atoms; R is selected from the group consisting of hydrogen, alkyl having up to five carbon atoms, R-substituted alkyl, hydroxyalkyl having up to ten carbon atoms; and n is a number from 3 to 9 which consists of contacting a nitrate having the structural formula where R is the nitrate ester of hydroxyalkyl having up to five carbon atoms and R is selected from the group consisting of hydrogen, alkyl having up to five carbon atoms, R-substituted alkyl having up to ten carbon atoms, the nitrate ester of hydroxyalkyl having up to 10 carbon atoms and R and the nitrate ester of hydroxy substituted alkyl having up to 10 carbon atoms with an esterifying agent selected from the group consisting of acetic anhydride, phthalic anhydride and lower aliphatic acid chlorides in the presence of an acid esten'fying catalyst to form an ester from the nitrate, contacting the ester with a mineral acid to form the alcohol.

7. The process which comprises reacting Z-(N-nitro- N-trinitroethylamino)ethyl nitrate with acetic anhydride in the presence of a mineral acid and hydrolyzing the product so obtained under acid conditions to obtain 2- (N-nitro-N-trinitro ethylamino ethanol.

8. The process which comprises reacting 3-(N-nitro- N-trinitroethylamino)-1-propy1 nitrate with acetic anhydride in the presence of an acid and hydrolyzing the product so obtained under acid conditions to obtain 3-(N-nitro- N-trinitroethylamino -1-propanol.

9. The process which comprises reacting 2-methyl-2- (N-nitro-N-trinitroethylamino)-1,3-propy1 dinitrate with acetic anhydride in the presence of a mineral acid and hydrolyzing the product so obtained under acid conditions to obtain Z-methyl-Z-(N-nitro-N-trinitroethylamino)-1,3- propanediol.

10. The process which comprises reacting Z-(N-nitro- N-trinitroethylamino)-1,4-butyl dinitrate with acetic anhydride in the presence of a mineral acid and hydrolyzing the product so obtained under acid conditions to obtain 2-(N-nitro-N-trinitroethylamino)-1,4-butanediol.

No references cited. 

1. COMPOUNDS HAVING THE STRUCTURAL FORMULA
 6. A PROCESS FOR THE PRODUCTION OF ALCOHOLS HAVING THE FOLLOWING STRUCTURAL FORMULA 